HUE030631T2

HUE030631T2 - Adhesion promoter for adhesive compounds comprising plastic and a polyisocyanate poly-addition product

Info

Publication number: HUE030631T2
Application number: HUE14166682A
Authority: HU
Inventors: Christian Renner; Gerlinde Tischer; Rolf Illguth; Margit Gehring; Franz Xaver Redl
Original assignee: Basf Se
Priority date: 2008-12-23
Filing date: 2009-12-10
Publication date: 2017-05-29
Also published as: US9914287B2; US20110250429A1; CN102264811A; BRPI0923623A2; EP2382261A2; ES2590211T3; CA2746833C; CA2936765A1; BR122019016061B1; EP2789649A1; CN102264811B; CA2936765C; CA2746833A1; EP2382261B1; MX2011006199A; EP2789649B1; WO2010072572A3; WO2010072572A2; MX354652B; BRPI0923623B1

Description

Adhesion promoter for adhesive compounds comprising plastic and a polyisocyanate poly-addition product

The present invention relates to composite elements comprising (?) plastic, adhering to which there is (ii) a polyisocyanate polyaddition product, where the polyisoeyanate polyaddition product is obtained via mixing of (a) isocyanate with PI Compounds havi «g groups reacti ve toward isoeyenafes, (c) catalysts, (d) Optionally Mowing agent, and (e) optionally further additives, to give a reaction mixture and permitting the reaction mixture to complete its reaction to give the pniyisocyanaie polyaddition product, where the compounds (b) having groups reactive toward isocyanates comprise a polyester polyalcohol as adhesion promoter, capable of production via polycondensation of an acid component and of one or more 1 ow - molecu!ar-weight diols whose molar mass is less than $00 g/moh in excess, where the tew-molecular*weight diets comprise at least 5 to 66 mol% of 1,3 -propanediol, based on the total amount of the dioi. The present invention also relates to a process lor the produetion of these composite elements, and to eotpponeots in the ütting-out of aircraft, of vehicles, or of buildings, and also to cable sheathing and other electronic components, e,g, in the construction of vehicles or in household cpMpmeftt, comprising this type of composite element.

Further embodiments of the present invention can be found in the claims, in the description, and in the examples. The abovementioned features of the subject matter according; to the invention, and the features thereof that will be explained below, can, of course, be used not only in the respective combination stated but also in other combinations, without exceeding the scope of the invention.

There are well-known polyisoeyanate polyaddition products which are obtained by mixing (a) isocyanate with (b) compounds haying groups reactive toward isocyanates, fe) catalysts, (d) optionally blowing agent, and (e) optionally further additives to give a reaction mixture and permitting the reaction mixture to complete its reaction to give the polyisoeyanate polyaddltion product, and there are also well-known composite elements involving said polyisoeyanate polyaddMoo products with plastic, Mechanical stressing of said composite elements, optionally after exposure to a high temperature and humidity, frequently leads to undesired break-away of the plastics from the poly isocyanate polyaddition products* Break-away of the polyisoeyanate polyaddition products írom the other plastics, with resultant irreparable damage to the composite .^lement, is not acceptable in particular for the use of such composite Clements in automobile construetion, where this type of stressing of these elements eaunof he excluded.

In the sheathing of electrical conductors, the insulated conductors are sheathed by a second pi.asie, eg, polyurethane. Said second plastic here has to adhere bn the insulation, so as to chsnre thai the system is watertight longitudinally with; respect to the arrangement of the electrical conductors. If the system here is not watertight, lit fs: impossible, in particular in automobile construction, to ensure separation between; a dry compartment and a wet cooxpartment. if an electrical line is invoiced which leads to control-module boxes or fuse boxes, or if encapsulation of relays and plugs is involved, there is also the risk of electrical short circuits. Sheathing moreover provides mechanical protection of the individual contact parts to prevent damage to and depol ing of these. ht order to ins prove the adhesion between polyi soeyanate polyaddition product and plastie, adhesion promoters based ott polyester polyalcohols are added to the reaction mixture. Components (h) to (e) are usually premixed in the form of polyol Component for the production of composite elements. The actual production of the polylsoeyaaate polyaddition products then takes place via mixing of the polyol component with an isocyanate component which comprises isocyanates |af, This procedure simplifies the production of the polyisocyanaie polyaddition iproduct, since there are then only 2 components to be handled, Composite dements of this type are described by way of example in IP 1361239. A disadvantage of the polyol comportent described ín EP 1361239 is that this forms a metaStahSe system at room temperature. If said polyol component is cooled to below about 14-18¾ o precipitate forms, and even if the polyol component is reheated to 2$°C it does not regain its homogeneity, Mowever, if inhomogeneous polyol mixtures are used for the production of the polyisocyanate polyaddition produel the result is low-quality products which then in some cases do not have any adhesion a t all to the plasti c of the composite, DB 100 22 276 and DE 100 22 280 disclose composite elements where the adhesion promoter is reacted together with isocyanate to give a prepolpuer having hydrojcy groups or, respectively, isocyanate groups, and this prepolymer is then séded ÍO the polyol component or, respectively, the isocyanate component. A disadvantage here is that a further operation is necessary in the production of the polyol component or, respectively, the isocyanate component. Furthermore, crystallization also taies place in the ease of pppoiymers comprising hydroxy groups and in the case of prepolyrners comprising isocyanate, and the stability and homogeneity of the components and of the system are then at Ésfe,

It was therefore an object of the present Invention to provide a composite element which is composed of polyisocyanate polyaddition products and plastic and which is easy to produce, and which has good adhesion between the poiyisocyanate pOlyaddiiiou products and plastic. A particular object of the invention was to provide composite elements whose eyeeUeuf mechanical properties permit, for example, their use in automobile construction, and whose adhesion between the plastic and the poiyisocyanate polyadditionproducts adherent thereto is not lost even when they are stored for 80 hours at 8P€ and 80% rel. humidity. A further object of the invention was to provide composite materials which can be used in the sector for insulation of electrical conductors and which have adequate adhesion to the insulation of the conductors prior to and after three periods of Storage, each of I hours, at '120*0 and 100% relative humidity, and which are watertight parallel to the direction of running of the eieelrieai conductors even after said heat-aging.

For the purposes of the present invention, a particular intention was that the composite elements he capable of production using starling components which give stable mixtures and which are therefore easy: to be used, and which can he used reprodueibly. A particular intention here was that, in the polyol component, compounds reactive toward isocyanates do not flocculate, even at temperatures below I5°C. Another object of the invention was to provide a process which can: produce composite elements of this type and which is easy to carry out.

The object according to the invention is achieved via composite elements comprising (i) plastic* adhering to which there is (ij) a polyisoeysnsfe polyaddition product, where the ppiyisocyanate polyaddition prodnet is obtained via mixing of (a) isocyanate with (b> compomtds having groups reactive toward isocyanates, (e) catalysts, (d) optionally blowing agent, and (e) optionally further additives, to give a reaction mixture and permitting the reaction mixture to complete its reaction to give the poiyisocyanate pblyaddliou product, where the compounds (b) having groups reactive toward isocyanates comprise a polyester polyakoho! as adhesion promoter* capable of production via polycondensarion of an acid component and of one or more low-rnoleculamweight diols whose molar mass is less than 500 g/moi, in excess, where the low-tnoleeular-weighf diols comprise from S to bő moi% of L.wpropanediol, based on the total amount of the diol.

The object accordini to the invention is further achieved via a process for ire production of composite elements comprising (i) plastic, adhering to which there is (il) a poiyisocyanate polyaddition product, where (a) isocyanate is mixed with (b) compounds having poops reactive toward isocyanates, (c) catalysts, (d) opfitmaily blowing agent* and (e) optionally further additives to give a reaction mixture and the reactionmixtureas permitted to complete its reaction to give the poiyisocyanate polyaddition product, where the compounds (b) having groups reactive toward isocyanates comprise a polyester pelyaleohof as adhesion promoter, capable of production via polycondensation of an acid component and of one or more 1 ow-molecular~weight diols whose molar mass is less than 500 g/mol, in excess, where the low-moleenlar'-weight diols comprise from § to 66 mol% of 1,3~propanédieî, based pn the total amount of the died.

For (he purposes of the invention, polyisoeyanate polyaddition products (ii) comprise in particular compact polyisoeyanate poiyaddition products, such as thermoseis or thermoplastic polyurethanes, and foams based on polyisoeyanate polyaddiion products, examples being flexible foams, semirigid foams, or iniepai foams, For the purposes of the invention, polymer blends comprising polyurethanes, and farther polymers, and also foams composed of said polymer blends, are to be understood as polyisocyanate poiyaddition products* The expressions “polyisocyanate poiyaddition product” ,an$ 'polyurethane” are used as synonyms for the purposes of the present invention, 1er the purposes of the invention, a compact polymetltao© is intended to mean a solid which is in essence free from gas inclusions. Further details concerning compact polyisoeyanate poiyaddition products according to the invention are found In "KunsfSfofThandhueh, Band 7, Polyurethane [Ilasies Handbook, volume % Polyurcthanesj”, Carl Hauser Verlag, 3rd edition 1993, chapter 8. thermoplastic polyurethanes are compact polyurethanes which: exhibit themmplastic properties. Thermoplastic properties here are understood to consist in repeated capability of the Thermoplastic polyurethane to melt on heating, with plastic iow, Further details concerning thermoplastic polyurethanes according to the invention are found in "Kunststoffoandhacij land 7, Bdiyprethane ||lastics Handbook, volume 7, Polyurcthanesj”, Carl Hauser Verlag, 3rd edition 1993, chapter S,2>

For the purposes of the invention, polyurethane foams are foams according to DIN 7720. The compressive stress at 10% compression, or, respectively, compressive strength to DIN 53 421/DIN EN ISO 604 of iextble polyurethane foams according to the invention here is 15 kPa or less, prcterably from I to 14|M and in particular from 4 to 14 kPa. The compressive stress at 103¾ compression of semirigid polyurethane foams aeeotdtng to the invention to DIN 53 4217PIM IN ISO fΘ4 is from greater than 15 to less than 80 kPa. The open-cell factor of semirigid polyurethane foams and flexible polyuréthane foams according to the invention to DIN ISO 4590 is prcterably greater than 85%, particularly preforahly greater than 90%. Further details concerning flexible fölyötÄipe foams and semirigid polyurethane foams according to the inveodee gre found in "KunstsiOflhandboch, Band 7, Polyurethane [Plastics Handbook, volume 7, Polyurethanes'j", Cat! Hauser Verlag, 3rd edition 1993, chapter 5.

Integral polyurethane foams are polyurethane foams to DIN 7726 with a mattinál none whose density is higher than that of the core as a result of the shaping process. The total envelope density averaged over the eefe and the marginal iene is preferably above 100 g/1 here. For the purposes of the invention, integral polyurethane foams can be rigid polyurethane loams, semirigid polyurethane foams, or ÜexíMe polyurethane foams. Further details concerning inlepal polyurethane foams according to the invention are found in Eunstsfoifoandhueh, Band 7* Polyurethane [Plastics Handbook, volume % Belyurethanespk Carl Hauser Verlag, 3rd edition 1993, chapter 7.

The composifo elements aeeordmi to the invention can comprise, as plastic (i ), by way of example thermo set plastic or therm op taste it is preferable to use thermoplastic, Cenventiohai thermoplastics comprise by way of example polyphenylene oxide (PPÖ), polyvinyl chloride (PVC), aerylonitrile-butadione styrene (ABS), polymeihyl methacry?ate (PMMA), aerylonitri 1 e-siyrene-acrylate (ASA), polycarbonate (PC), thermoplastic polyurethane (ÍPUfc polyethylene (FB), polypropylene (PF), The composite elements preferably comprise, as plastie (i), thermoplastie polyolefins (TPO), such as polyethylene and/or polypropylene, polyvinyl chloride (PVC), styrene-maleic anhydride (SMA), and/or a polycarhd«aie/siyrene-acry!onltfile/acrylonitrile-bntadiene blend (PC/ABS), preferably in the form of foils or sheets, or in the form of braided material.

The plastics (i) can be used in the form of conventional materials for the production of the eomposite elements, for example in the form of sheets or foils, generally with a thickness of front 0.2 to 2 mm.

Foils of this type are commercially available, and their production is weihknowu. The thickness of the foils is preferably from 0.2 to 2 mm. It is also possible to use, ss fi), foils comprising at; teást two foyers, where, for example, ooe of the loyers eotoptees ah -àMA ând/ftf polycarbonate material.

Plasties (i) moreover comprise all of the conventional plastics-hased materials which are usually used lor the insulation of electrieal eondnctora. These comprise polyvinyl chlorides (PVC.), thermoplastic polyurethane (TPU ). polypropylene tPP)s and ethylemfoeirafluoroethylene (ETFE).

The plastics (i) composed of styrene-maleic anhydride (SMA) and/or a po!yeaihooate/st}nxuiC"acrylonitrile/acrylonitîile-bufadieî\e blend (PC/ABS) can bo used in the form of eoftvenitöhal materials for the production of the composite elements, for example in the form of sti ffening part for instrument panels or door-side parts. Skin materials for the same application are often composed of thermoplastic polyolefins ffPOs) and polyvinyl chloride (PVC).

According to the invention, the polyisoeyahaie polyadditloft products (ii) adhere to the plastic (i). The production of said polyisoeyaftate polyaddition products (ii), preferably of the polyurethanes, tabes place via mixing of (a) isocyanate with (b) compounds having groups reactive toward isocyanates, (c) catalysts, (d) optionally blowing agent, and (e) optionally further additives to give a reaction mixture and perftntdng the rcaeion mixture to complete its reaction to give the polyisocyanate polyaddition product, where the compounds (b) having groups réactivé toward isocyanates comprise a polyester polyaleohol as adhesion promoter capable of production via polycondensation of an. acid component and of one or more low-molecular-weight diols whose molar mass Is less than 500 g/moi, in excess, where the low- mol ecu I ar-w e; glu diols comprise from 5 to 66 tnol% of lvitepfoponedteh hased on the total amount of the diol,

For the purposes of the inveotion, the mixture of components (a) to (c), and also, if present, (d) and (e) is termed reaction mixture when conversions in the reaction are smaller than 90%, preferably smaller than 80%, based oft the isocyanate groups.

The isocyanate (a| used ihr tie production of the composite mtWA abÄdfei. to the mventtott comprises any of the polyisocyanates known for the production Of polyurethanes. These comprise the aliphatic, cycloaliphatic, and aromatic hi - or polyfenetlonalized isocyanates known from the poor art, and also any desired mixtures thereof. Examples are diphenyimethanc 2,2'--, 2,4\ and 4,4 -dhsocyanatev the mixtures composed of monomeric di phenyl m ethane diisocyanates and of homologs of diphenyimethane diisocyanate having a larger member of rings (polymer MDI), isophorone diisocyanate (IPDI) or its oltgornefS^ tolylene 2,4- or 2*&"dilseeyaniie (TDI), or a mixture of these, tetramethylene diisocyanate or its oligomers, hcxamethylene dilsoeyanatc (HB1) or its uligmners, or .naphthylenc diisocyanate (NDÍ), or a mixture thereof.

It is preferable to use 4,4f~MDl and/or HDI, or else homologs of diphenylmethane iisoeyanate haying a higher number of rings, 4,4’~MDI is particularly preferably used in mixtures with PMDI and can comprise small amounts, up to about 10% by weight, of uretdione-, allophanate-, or uretoiiimlne-rnodihed polyisocyanatcs, Other possible isocyanates are described by way of example in ‘‘Knasisieffhandhuch, land ”, Polyurethane [Plasties Handbook, volume 2, Polyurethanes]”, Carl Hät» Verlag, 3rd edition 1993, ehapterl.2 and 3.3,2.

The isocyanate (al can he used in the form of poiyisoeyanafe prepolymers. Said polyisocyanate prepolyrners are obtainable by reacting an excess of polyisocyanatcs described above (constituent (a-1 )), with polyols (consituent (a-2)} tor example at temperatures of from 30 to 1()8¾ preferably at about|0°C, to give the prepolyrner.

Polyols (a -2) are Inown to the person Skilled in the art and are described by way of example in ‘‘Kunststoffhandhuch, ?, Polyurethane [Plastics Handbook, 7, PoIyurethanesf\ Carl Hauser Verlag, 3rd edition 1993, ehapfer 3.1, By way of example, therefore, it is also possible that the polyols used also comprise the polyols described below under (b). ft |5s lalso optionally possible to all chain extenders or crosslinking agents (a-3} to the reaction to give the polyisoeyanaie prepolymer, Suitable chain extenders tor the ; prepolymer are dihydrie alcohols, and suitable crosslinking agents for the prepolymer are trihydric alcohols, examples being dipropylene glycol and/or tripropylene glycol,, or the adducts of dipropylene glycol and/or tripropylehc glycol ^ith alkylene oxides, preferably propylene oxide.

Compounds used having groups roaetive toytard isocyanates can comprise any of the compounds which have at least two hydrogen atoms reactive toward isocyanate. By way of example, it is possible to use compounds of this type whose functionality l§; froth 2 to I and whose molar mass Is front 500 to 12 000 g/mul, preferably from 1000 to 0Ö00 g/moL By way of exampieytherefete, if is possible to use polyether polyamines, po 1 ycarbonatedioIs and/or polyether poiyol% polyester polyalcohol polyols, or a mixture thereof*

Polyetherols are by way of example produced from epoxides, such as propylene oxide and/or ethylene oxide, or torn tbfeabydfoih'aOj using starter compounds having active hydrogen atoms, examples being aliphatic alcohols, phenols, amines,i Carboxyhb'aeids,: wafer, or compounds based on natural substances, e.g< SUCreM* Sorbitol, or mannitol, with use of a catalyst. Mention may be made here of basic catalysts or of double-taeial-eyanide catalysts, for example as deseribed in PCT/EF2Ö05/010124, EP 90444 or WO 05/090440.

Polyester polyaleohol polyols are by way of example produced from älkaeepolycafhoxylie acids, preferably aikunediearboxyie acids, and an excess of alcohol and polyhydrtc alcohols, poiyihioeiher polyols, poiyesteratnides, polyaeetals containing hydroxy groups, and/or aliphatio polycarbonates containing hydroxy groups, preferably in the presence of an esterification catalyst. Other possible polyols are given by wav of example in “Kunststofihandbuch, Band % Polyurethane [Plasties Handbook, volume 7, Polyurethane»!’’, Carl Hauser Verlag, 3rd edition 1.993, chapter 3/.1, U is preferable diát the polyethet alcohols (b) used, in particular in the production of flexible foams and of semirigid foams, comprise pel vethet alcohols whose average füfiéíioMíite is froth | to 3 and whose OH number is from Id to $0 mg ItQH/g, and also that the adhesion promoters used 'comprise the preferred amounts described to the introduction of the polyester polyalcohol alcohols aecording fo the invention and deserihed in the introduction. Polyethern Is and their preparation for example via aikoxylation of conventional starter substances, are well known. for flexihlo integfal systems or compact systems, where either of these is used for cable sheathing or for eneapdlation of plugs, it is preferable to use mixtures compesed of polyether aleohols whose average fonctlonality is from 1.5 to 2.5 and whose OH number is from 20 to 50 mg KOH/g with polyether alcohols whose average functionality is from 2 to 3 and whose ©H number is from 2.0 to 50 mg KOH/g, andl also with chain extenders. It is also possible to use graft polyols.

The compounds fb) according to the invention can moreover he used in a mixture with chain extenders and/or with efosslinking agents, as compounds react!ve toward isocyanates. The chain extenders are usually dihydric alcohols whoso molar masses are from 60 g/mol to 499 g/mol, examples being ethylene glycol, propylene glycol, IpfoutanodioT or 1,5-penianediol. The crosslinking agents are uSUdlly oompourids whose molar masses are from (>() g/mol to 499 g/mol and which have 3 or more active hydrogen atoms, preference being: given here to amines and particular preference being given hère fo alcohols, such as glycerol, trimeth viol propane, and/or pentaerythritol, and also aikoxylation produets of the||. It is preferable to use crosslinking agents whose functionality toward isocyanates is 3 and whose OH number is greater than 500 mg KOH/g, preferably greater than 900 mg KOH/g, particularly preferably greater than 1200 mg KOH/g,

The adhesion promoters used comprise polyester polyalcohols which can be produced via polycondensation from an acid component and from one or more low^moleenlor-weight diois whose molar mass is less than J00 g/mol, in excess, where the low-moíecuíar-weight diols comprise from 5 to 66 raol%, preferably

frûm 10 to SO moi%, of I ,3~propanediol, based on the total amount of the diof It is preferable that the acid: component here comprises at least 90% by weight, particularly prefteahly 93% by weight, and m particular 100% by weight, of adipic acid. Tbc d fols tere preferably comprise at least one further diol alongside propanediol, selected front the group consisting of monoethyiene glycol, 1,4-hutanediol, 1,5-peníanedíbk und l,6diexanedioL

The hydroxy number of the adhésion promoter is preferably from 40 to 100 mg KOllg, preferably írom 4| to 80 mg KOH/g, and particularly preferably from 50 to 65 mg mmilg. The proportion of the adhésion promoter is from Ô.Î to 15% by weight, preferably from 0.5 to 10% by weight, and particularly preferably from 0,8 to 584 by weight, based on the total weight Of the eompoimd (h) having groups reactive toward isocyanate. The adhesion promoters according to the invention are easy to process and have viscosities at 75%’ which are smaller than 2000 mf^s, preferably smaller than 1500 tnPas, and particularly preferably smaller than 1200 rnPas,

Catalysts (c) that can he used comprise eonventional compounds which by way of example markedly accelerate the reaction of component (a) with component (b). Examples of those that can be used are tertiary amines and/or organorneiailic compounds well known for this purpose. Mention may be made by way of example of amidines, such as 2,3~dimethyl~3,4,5,6-4etrabydmpyrimidine, tertiary amines, such as tnetliylamine, tributyl amine, dimei.hy 1 benxy\amine, N-methyI~, N-ethyl··, and N-cydobexytmorpholin«, N,N.N8N4tetrantethykchylcnedianűne, MsM,W',l4ktmrameihylbaianediamme, N,HsM^MetfamÄptexanediam!ne, pentatnethyidiethylenetriamine. tetramethyldiaminoethy] ether. hisfdimethylamißöpropyi)urea, dimethylpiperazino, l,2-dimefhylímida2öle, I-axahieydo [3.3.0] oct an e, and preferably 1,4 - di axah i eycl o [2.2.2] octane, and alkanol amine compounds, such as triethanolamine, triisoprppaooianrtne, N> methyl·- and/M-elhyldiethanolamlne, asé.jínaethylithantpiamtne. Equally, use may he made of organometallie compounds, preferably organotin compounds, exampies being stannous salts of organic carboxylic acids, e.g. stannous acetate, stannous octoate, stannous ethylhexoate, and stannous laurate, and the dialkyltin (!¥) salts of organic carboxylic acids, e.g. dibmyltin di acetate, dibutyitin dilaurate* dibutyitin ntaieate, and dioefyltin diacetate* and also bismuth carboxylates, such as bismuth(Hl) neodeeanoate, bismuth: «d· bismuth oetanoate, or a .mixture thereof. The organomeiallie compounds can be used alone or preferably in combination with strongly basic amines. If component (b) k uh use exclusively amine catalysts.

Prefered catalysts used are those which give minimum fogging (DIN 75201), and also low ¥€>£ and log values (VH& 278), be, minimum emission of volatile compounds írom the foam. It is preferable to use, as catalysts (c), compounds which aro reactive toward isocyanates, i.e. by way of example which have a free hydroxy group and/or a free amino group. Compounds of this type are well known and have been widely described. By way of example, d i methyl amin opropy ! am i ne, N,N,N-trimethy1-N-hydroxyeihylbis{aminocthyl) ether, auiipppropylimidazole and/or 2'-propanolbis(3~dimethylan««opropyT)aTriine can be used, lit particular the production of/semirigid foams is preferably carried out in the absence of catalysts containing tin. The amount used of salts of onlboyylie acids, for example potassium acetate, as catalysts (e) Is preferably smaller than 0,21% by weight, particularly preferably smaller than 0,15% by weight, based on the total weight of the compounds (b) reactive toward isocyanates.

The blowing agents (d) used for the production of theMamedgolyisneyanate polyaddition products according to the invention can comprise well-known compounds having chemical or physical action. A preferred blowing agent that can be used having chemical action is water, which forma carbon dioxide via reaction with the isocyanate groups. Examples of physical blowing agents, i.e. those inert compounds which vaporize under the conditions of polyurethane formation, are (cyclo)ahphatie hydrocarbons, preferably those having from 4 to 8, particularly preferably from 4 to 6 and in particular 5, carbon atoms, partially halogobaied hydrocarbons, Or eibem, ketones, or acetates. The amount of the Mowing agents used depends on the desired density of the foams. The various blowing agents can be used individually or in any desired mixtures wft one another.

As blowing agent (d) for semirigid foams it is preferable to use water, its mnouot preferably being from 1% by weight to 5% by weight, particularly preferably írom 1.5 to 3% hv weight, based on the total weight of the compounds (b) reactive toward isocyanates. In the case of flexible integral foams it is likewise preferable fo use water, itsamount preferably being from 0% by weight to 0.8% by weight, particularly preferably from 0,07 to 0,3% by weight, based on the total weight of the compounds reactive toward isocyanates. Physical blowing agents are also orten used for flexible integral foams, in the event that a compact product Is to be produced as polyiso cyan ate polyaddition product, no blowing agents are used.

The reaction optiooaly takes place in the presence of (e) additives, e.g. fillers, fibers, e,g. In the form of wovens and/or mats, cel! regulators; surfactants, and/or stabilizers with respect to oxidative, thermal, or microbial degradation or aging. If is preferable that the productioa of the foams according to the invention tabes place In the presence of well-known emulsifiers, which retain the phase-stability of the polyester polyalcohol according ίο the invention in the preferred polyeiherol as component (b).

The produefion of fhe cornpositc elements according to the invention takes place by bringing the reaction mixture for the production of the polyisoeyanate polyaddition products (ii) into contact with the plastic (i), usually without the use of further materials generating adhesion, for example adhesives. It is preferable that plastic (i) and polyisoeyanate polyaddition product (ii) are brought into contact with one another in the eondifion where reaction has not been completed, It Ii particularly preferable that, for the production of the composite elements according to the invention, the reaction mixture lor the production of the composite elements according to foe Invention is brought into contact with the plastic (i), for example in a mold, in other respects, the production of the polyisoeyanate polyaddition products which ean optionally comprise isoeyaourate structures and/or urea structures, for example of the flexible foams, semirigid foams, or integral foams, particularly preferably of the semirigid foams and integral foams, takes plane by web-known processes, for example the one-shoi process, using well-known tooling, molds, mixing apparatuses, and feed egnipment.

Pot the production of the products according to the Indention, the isocyanates (a) and the compounds (b) reactive toward isocyanates and optionally (d) can be reacted in amounts such that the equivalence ratio of W€T) groups of (a) to the total number of the reactive hydrogen atoms of <b) and optionally fdyis preferahly from 0.3 to 1,8:1, particularly preforably from 0,7 to 1.3:1, and in particular fount Ö.9 to 1,1:1. The reaction to give foe product can by way of example be carried out via manual casting, or via high-pressure or low-pressure machinery,; for example via RIM processes freaction injection molding) in closed or preforably open molds. Suitable processing machinery is available commercially, The starting components are usuallyj as a fonction of the application, mixed at a temperature of ltom 0 to IBtRCl preforably ltom 20 to itPCl and by way of example mUoduaed info foe mold. The plastic (i) here is preferably inserted: into the mold prior to the introduction of the reaction mixture. The mixing of components (a) to (e) can, as previously described, be carried out meehanieally by means of a Stirrer or a mixing screw, or can take place in a conventional high-pressure mixing head. By way of example, the reaction of the reaction mixture can take place in conventional, preforably fomperslure-controliabfo and scalable molds. The molds used for foe production of the prod acts can comprise conventional and commercially available tooling, the surface of which is composed by way of example o f steel, aluminum , enamel, Teflon, epoxy resi n, or another polymeric material and the surface here can optionally have been chromed, for example hard"chromed, The molds should preforably he temperature-eontroflahfo m order to permit setting of the preferred temperatures, sealable, and preforably equipped to exert a pressure on the product. The mold temperature at which the reaction to give foe polyurethane foams usually fakes place, and this is also foe preferred temperature of the starting compehenta·» is from 20 to 22O'Tl preforably from 25 to 121F€, particularly preferably lots ,3# to mx, and the reaction time here is aseaily J to 30 min. preferably from. ! fe 5 min, it has proven advantageous to produce the polyurethane foams by the two-component process, arid to combine the compounds (b) reactive toward isocyanates and optionally the catalysts: (e), and optionally blowing agent fd), and/or additives (e) in the A component, and to use the isocyanates (a) and optionally catalysts, and/or blowing agents as 8 component.

By virtue of the see Of tile polyester polyalcohol polyols described in the introduction, the composite elements according to die invention in particular have muri: edly improved adhesion between plastic (i) and polyisocyanate polyaddition product fit}, this adhesion Oati he determined in various ways, tor example via measurement of the three needed to peel the plastic. In the ease of sheet- like ft is preferable that the peel force achieved between (0 and p), measured to DIN 53289 or 5353% in new condition, and also after storage in hot and humid conditions, is 2,5 N/Crn or more. The adhesion can also he determined by using subjective assessment criteria, la the case of encapsulation of cables and in the ease of bushings, the system is only watertight ioogitudtoaiy if there is adhesion between (i) and (ii). This is Checked by way of example to the internal specification of DELPHI (REl-WDP 1), .the int^MIÂ'àp^ïS^ÂM: ôl.Bhfd or the PSA Peugeot. Citroen standard (B21 7850). A column of water is pincéd on one side of the bushing here; if there is any measurable moisture on the other side of the hushing, the specimen does not pass the test. Teats using elevated air pressure are moreover carried out in some eases to test whether cable sheathing is leakproof, the pressure drop being measured.

The composite elements according to the invention are preferably used as components in vehicle construction, aircraft construction, or the construction of buildings, for example in the ferih Of dashboards, door cladding, parcel shelves, consoles, armrests, or door mirrors. The composite elements according to the invention are also used in the sheathing of electrical conductors. Here, mention may he made not only of the production of dimensionally stable foam-encapsulated cable sets but also of the production: of bushings* and of the encapsulation of plugs and of relays. For products in vehicle construction, aircraft construction or the construction of buildings, and also In the insulation of electrical conductors, the polyisoeyanate polyadditien product hero preferably tales the form of a foamed product, hi the encapsulation of plugs and of relays, the polyisoeyanate polyaddition product is preferably in compact form.

According to the invention, flocculation or crystallization of the polyester polyaieohofs from a mixture with compounds (h) reactive toward isocyanates can ho suceessltlly avoided by using the polyester polyaleohols according to the invention, if crystallization takes place, the intention is that the precipitate dissolves on reheating to room température. Furthermore, the viscosity of the mixture at low temperaturos is markedly lowered when, comparison is made with mixtures using conventional polyester polyaleohols, thus improving their processability. Examples are used below to illustrate the Invention.

The table below shows a selection of the polyester polyols which wore produced tur the object according to the invention and were tested for tempnralnm-ehange behavior, for adhesion and also optionally for stability in the polyol component.

The ibnetionahfy of all of the abovementioned esters is 2, and their OH numbers are from 50 to 65 mg KOH/g. The pour points or crystallization temperatures of the pure substances were first determined at cooling rates of I °C/day ;

The polyesters using propanediol, specifically those having amounts of propanediol smaller than 50 mo.l%* based on the total amount of diof. exhibit a markedly reduced pour point or crystallization point.

Adhesion to PC A1S sheets was studied. For this, 2 different qualities of sheets were used; Sheet 1 î giasshherwmmibreed PC/ABS

Sheet 2; FC/ABS without glass fiber reinforcement

Adhesion was assessed using a subjective test method. The polyurethane here was peeled from the PC/ABS sheets, and adhesion was eyaíuateffilö: Ihe basis- of'äü· evaluation scale of 1 to 5. Key: 5 adhesive fracture; no adhesion 4 cohesive fracture; skin can easily he removed from the PC/ABS sheet f cohesive if aCture; skin can he removed from the PC/ABS sheet 2 cohesiveffaeture; iskin can be rethoved with difficulty from the PC/ABS sheet I cohesive ifacture; skin eannoi le removed from the PC/ABS sheet

Adhesion írom: .M is : generally sufficient tor1 automobile applications.

Adhesion Is evaluated here 10 minutes, 1 hour, and 24 hours after the production process* and also after aging in hot and humid conditions (8()¾ 80 hours, 80% relative humidity).

Various systems are studied heinw* using the Mowing starting maferiais:

Polyol A: Polyether polyol with OH number 28 mg KOH/g, PO/EO ratio by weight 86:14, average 1¾¾ctionaiity 2.7'

Polyol 1: Polyether polyol with Oil number 36 mg K.OH g, PO/EO ratio by weigh! 87:13, average functionality 2.6

Polyol <2: Polyether polyol with Oil mint her 250 mg KOH/g, only PÛ, average functionality 2.0

Polyol D: Polyether polyol with Oïl number 36 tug PO/EO ratio by weight 94:6, average functionality 2.2

Polyol E: Polyether polyol with Oil nutnber 535 mg KOH/g, only Sh average fííüotieoaltty 3 J

Polyol f: Polyether polyol with OH number 35 mg KOH/g, PO/EO ratio by weight 86:14, average fonetionality 2i7

Polyol O: Polyether polyol with Oil oumber 26 mg KÖH/g, PÖ/EO ratio by weight 79:21, average functionality 2.5

Polyol H; Polyether polyol with OH number 555 mg KOH/g, only PO> average functionality 3.0

Polyol I: Polyether polyol with OH number 29 mg KOH/g, PO/EO ratio by ^elgM:i.|tl9i,:.:^trage functionality 1.8 PP 50: Perstorp polyol with OH number 630 and Emotionality -4

Jeffoat ZE.5Ö: amine catalyst IfOtu Huntsman, reactive toward isocyanate Jeffoat 2110: amine catalyst troth Huntsman, reactive toward isocyanate Polycat 15: amine catalyst from Air Products, reactive tow ard isocyanate Isocyanate A:base-level MDI with functionality 2,1 and KCO content 26 wiife^ictionuHty 2,1 and NCO content 25 PMOl; Polymer MDI with averap functionality 2.7 and NCO content 31.2

The formulations for systems 1 and 2 are collated in the table below, where the quantitative data are based on parts by weight:

MR ! 00 here mesas mixing ratio in parts by weight of isocyanate component relative to ! 00 parts of polyol component

The results of the: adhesion, test are shown, in the two tables below;

From the examples it can be seen that adhesion using the polyester polyols eoitpisiii thé; polyesierols having I,3~pmpanediol as died is at least similar to or hotter than adhesion using the reference polyols* Although esters having 10% of seooinie acid, based on the A component, exhibit equally good adhesion, the desired resistance to temperature change is achieved only for relatively large-amounts (20%, based on the add component), and there is marked impairment of adhesion when such large amounts ate used, and use of succinic acid is therefore not advisable. It is moreover apparent that relatively large amounts of an add other than adipic acid reduce adhesion.

Clouding of the polyol eom|tment was studied by taking the following systems as an example, the quantitative lata here being based on parts by weight:

The various polyesters were used tft systems 3 arid 4 arid cooled, at a cooling rate of PC/day m a separating tunnel. The observed results were as follows:

Claims

Adtiéztónövető hatóanyag, műanyagot és potlfxeóiartát polfaddieiés terméket tartalmadé ragaszté-kompezitok számára mmmmMi igénypontok 1*. Kompozít etem, amely tartalmaz (I) műanyagot, amelyhez ragasztva 01) agy poliizocianát poliaddíciós termék kapcsolódik, ahol a poliszodénál poliaddi-cios terméket a) izocianátnak b) az ízocianátokkal szemben reaktív csoportokkal rendelkező vagyöletekkel, c) katalizátorokkal, 0} adott esetben hordozóanyaggal és e) adott esetben további adalékanyagokkal való elkeveréséveí állítjuk elő, amellyel egy reakcióelegyet kapunk, és a reakdoelegynek lehetővé tesszük a reakció lejátszódását, amellyel a poliizocianát poliaddíciós terméket kapjuk, ahol az izoclanátokkal szemben reaktív csoportokkal rendelkező vegyületek (b) adhéziónö-velő hatóanyagként tartalmaznak egy poliészter-poiialkoholt amely pokkondenzá-dóval képes egy sav-komponens és egy vagy több olyan klsmolekulatőmagú dióinak feleslegben való termelésére, amelyeknek moltömege 500 g/mol-nál kisebb, ahol a kismolekulatőmegű dioiok, a diói teljes mennyiségét véve alapul, 5-68 mo!% 1,3-propán-dlolt tartalmaznak.Includes additive tracking agent, plastics, and polyphosphate polyphadate for product adhesives, mmmmMi 1 *. Composite element comprising (I) plastic bonded to 01) is attached to a polyisocyanate polyaddition product of the brain, wherein the polysodene product is a polyaddioid product a) isocyanate b) with properties having reactive groups against cyanocyanates, c) catalysts, 0} optionally with a carrier and e) optionally, mixing with additional additives to form a reaction mixture and allowing the reaction mixture to complete the reaction with which the polyisocyanate polyaddition product is obtained, wherein the compounds having reactive groups against isoclanates (b) contain a polyester as an adhesive agent. polyol which is capable of producing excess acid component and one or more nucleated nuclei having a mole weight of less than 500 g / mole, based on the total amount of diol of diols, based on the total amount of nuts. Containing from 5 to 68% by weight of 1,3-propanediol.

2. Az 1. igénypont szerinti kompozít elem, azzal jellemezve, hogy a savkomponens tartalmaz legalább §0 tömeg % ad ip insavat.Composite element according to claim 1, characterized in that the acid component comprises at least 00% by weight of ad ip insava.

3, Az 1. vagy 2, igénypont szerinti kompozít elem, azzal jellemezve, hogy a dioiok tartalmaznak legalább egy további dlolt, amelyet a monoetiién-giikol, 1,4~bu-tán-diol, 1,5-pentán-diol és az 1,8»hexámdioí által alkotott csoportból választunk ki, 4 Az 1~3. igénypontok bármelyike szerinti kompozít elem, azzal jellemezve, hogy az adhézíónövelö hatóanyag hidroxi-száma 40-től 100-ig terjed, S, Az 1-4, Igénypontok bármelyike szerinti kompozít elem, azzal jellemezve, hogy az adhézíónövelö hatóanyag hányada, az ízocianátokkál szemben reaktiv cső portokkal rendelkező vegyüfet (b) össztömegét vevő alapul, 0,5 tömeg%-túl 10 tő-meg%~ig terjed. S, Az 1-5. igénypontok bármelyike szerinti kompozit elem, ázzál jellemezve, hogy a (ii) políizocianál poiiaddiclős termék egy kompakt poliuretán, egy flexibilis po-liuretán báb, egy félig merev poliuretán hab vágy egy integrális hab. 7« Az 1-6. igénypontok bármelyike szerinti kompozit elem, azzal jellemezve, hogy az (!) műanyag egy termoplasztikus műanyag.Composite element according to claim 1 or 2, characterized in that the diols contain at least one further dlol, which is monoethylene glycol, 1,4-butane diol, 1,5-pentanediol and \ t It is selected from the group consisting of 1.8 "hexamido", 4. Composite element according to one of Claims 1 to 4, characterized in that the hydroxyl number of the adhesive agent ranges from 40 to 100, S, The composite element according to any one of Claims 1 to 4, characterized in that the proportion of the adhesive agent is reactive against the flavourant. the weight of the compound (b) having a tube port is based on the customer, ranging from 0.5 wt% to 10 wt%. S, 1-5. Composite element according to one of Claims 1 to 5, characterized in that the polyisocyanal polyidocyanate product (ii) is a compact polyurethane, a flexible polyurethane puppet, a semi-rigid polyurethane foam desire as an integral foam. 7 «The 1-6. Composite element according to one of Claims 1 to 3, characterized in that the plastic (!) is a thermoplastic plastic.

8. Az 1-7. igénypontok bármelyike szerinti kompozit elem, azzal jellemezve, hogy az (i) műanyag egy elektromos vezető számára szolgáló szigetelő,8. Referring to Figures 1-7. Composite element according to one of Claims 1 to 3, characterized in that the plastic (i) is an insulator for an electric conductor,

9, Eljárás olyan kompozit elemek előállítására, amelyek tartalmaznak (í) műanyagot, amelyhez ragasztva (ri> egy poliizocianát poiiaddiclős termék kapcsolódik, ahol a) izooíanátoí elkeverünk b) az izocíanátokkal szemben reaktív csoportokkal rendelkező vegyOietekkel, c) katalizaforokkaí, d) adott esetben hordozóanyaggal és e) adott esetben további adalékanyagokkal amellyel egy reakdőelegyet kapunk, és a reakcióelegynek iehetove tesszük a reakció lejátszódását, amellyel a poliizocianát poliaddlelós terméket kapjuk, ahol az izocíanátokkal szemben reaktív csoportokkal rendelkező vegyüietek (b) adhéziónö-veiő hatóanyagként tartalmaznak egy poliészter-polialkoholt, amely poiíkondenzá-dőval képes egy sav-komponens és egy vagy több olyan kismolekuiatomegű dióinak feleslegben való termelésére, amelyeknek moltömege 500 g/mohná! kisebb, aboi a kísmolekuiatőmegű dsoiok, a diói teljes mennyiségét véve alapúi, 5-68 mof% 1,3-propán-diolt tartalmaznak,Process for the production of composite elements comprising (ii) a plastic bonded to (i.e. a polyisocyanate polydicylate product, wherein a) isolate is mixed with (b) the oxoethane having reactive groups against the isocyanates, (c) optionally with a carrier; and e) optionally adding additional additives to form a reaction mixture and reacting the reaction mixture to obtain the polyisocyanate polyaddylate product, wherein the compounds having reactive groups against isocyanates (b) comprise a polyester polyalcohol as an adhesive active agent. is capable of producing an excess of an acid component and one or more low molecular weight nuts with a polyol condenser having a molecular weight of 500 g / mohn. having a lower molecular weight dsii having a total of 5-68 mof% of 1,3-propanediol based on the total amount of nuts;

18. Szerkezeti elem repülőgép-, közlekedési eszköz- vagy épületek építésében, amely tartalmaz egy, az 1-9. igénypontok bármelyike szerinti kompozit eiemet. 11, A 10. igénypont szerinti szerkezeti elem, azzal jeiiemezve, hogy ez egy elektromos vezető védőburkolata.18. A structural element in the construction of aircraft, means of transport or buildings comprising one or more of the embodiments 1-9. Composite according to any one of claims 1 to 3. A structural element according to claim 10, characterized in that it is a protective cover for an electric conductor.